Process for preparing monoazo dyestuffs



United States Patent 3,419,541 PROCESS FOR PREPARING MONOAZO DYESTUFFSRudolf Kiihne and Fritz Meininger, Frankfurt am Main,

Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormalsMeister Lucius & Bruning, Frankfurt am Main, Germany, a corporation ofGermany No Drawing. Continuation-in-part of application Ser. No.256,247, Feb. 5, 1963. This application July 28, 1964, Ser. No. 385,772

Claims priority, application Germany, Feb. 8, 1962, F 35,973 The portionof the term of the patent subsequent to Feb. 8, 1983, has beendisclaimed 3 Claims. (Cl. 260-462) ABSTRACT OF THE DISCLOSURE Processfor the manufacture of reactive monoazo dyestufls containing as reactivegroupings at least one of the groupings 1' 1 1?: NSOrOHnOH-OSOaH '111'12 -N-SO:-CH2-CHCl l -r -NSOa-OH=CHR in which R represents lower alkylor benzyl, R represents hydrogen or lower alkyl, wherein monoazodyestuffs in which R, is hydrogen are reacted with an alkylating agent.The dyestuffs obtained thereby are suitable for the dyeing or printingof cellulose, protein, polyamide and polyurethane fibers.

This application is a continuation-in-part of our copending application,Ser. No. 256,247, filed Feb. 5, 1963, and since abandoned.

The present invention relates to monoazo-dyestulfs containingN-alkylated ethionylamino, fl-chloro-ethanesulfonyl-amino orvinylsulfonylamino groups and to a process for their manufacture.

It has been found that monoazo-dyestufls containing N alkylatedethionylamino, p chloro-ethane-sulfonylamino or vinylsulfonylaminogroups which, in the free acid form, having one of the following generalformulae wherein D represents a monoor binuclear aryl radical, forexample a radical of the benzene, naphthalene or diphenyl ether series,which may be substituted, in particular, by sulfonic acid groups, e.g.,phenyl, chlorophenyl, lower alkyl phenyl, di-lower alkyl phenyl, loweralkoxy phenyl, lower alkoxy sulfophenyl, trifluoromethyl phenyl,carboxyphenyl, sulfophenyl, disulfophenyl, acetylamino sulfophenyl,naphthyl, K represents the radical of a coupling component, for instanceof the benzene, naphthalene or pyrazolone series or of the acetoaceticacid, e.g., hydroxynaphthyl, sulfohydroxynaphthyl,disulfohydroxynaphthyl, disulfoarnino naphthyl, acetylaminohydroxynaphthyl, acetylamino sulfohydroxynaphthyl, acetylaminodisulfohydroxynaphthyl, lower alkylamino hydroxynaphthyl,acetoacetylaminophenyl or 1 chloro-sulfophenyllower alkyl-5-pyrazolone,X stands for a direct linkage or one of the groupings R represents alower alkyl group or an aralkyl group, R represents a hydrogen atom or alower alkyl group, and n and m stands for 0, 1 or 2, the sum of rr+mbeing 1 or 2, can be prepared by reacting monoazo-dyestuifs having oneof the following general formulae h [Xl IsoroH=OH-Rr]m wherein D, K, X,R n and m. are as defined above, with alkylating agents in an aqueousmedium in the presence of an acid-binding agent.

The monoazo-dyestufis which, in the process of the present invention,may be used as starting materials may be prepared in known manner bycoupling any diazo component of the benzene, napthalene or diphenyletherseries with any coupling component, whereby the diazo and/or thecoupling components are elected in a manner that the ready dyestuffscontain in the diazo or in the coupling component or in both components:at least once an ethionylamino, fi-chloro-ethanesulfonylamino orvinylsulfonylamino group.

When carrying out the process of the present invention, the dyestuffsused as starting material are dissolved in water or, in case they aresparingly soluble or insoluble in water, suspended therein in a finelydivided form, and reacted at a temperature of between about 30 C. andabout C. in the presence of an acid-binding agent in the neutral orweakly alkaline range with an alkylating agent, While vigorouslystirring.

As alkylating agents there may be used alkyl halides, such as methyl andethyl bromide, or aralkyl halides, such as benzyl chloride, or dialkylsulfates, such as dimethyl sulfate and diethyl sulfate.

As acid-binding agents there may be used alkali metal or alkaline earthmetal hydroxides, borates, phosphates or acetates, especially alkalimetal or alkaline earth metal. carbonates or hydrogen carbonates, suchas potassium hydrogen carbonate, sodium carbonate or calcium carbonate.

The monoazo-dyestuffs containing N-alkyl-vinylsulfonylamino groups canalso be prepared directly from the dyestuffs used as starting materialwhich contains N- ethionylamino or ,8-chloro-ethane-sulfonylaminogroups. The preparation of the monoazo-dyestuffs containing N-alkyl-vinylsulfonylamino groups may be carried out, for example, byreacting the dyestuffs used as starting matenial which containN-ethionyrlamino or [ichloro-ethane-sulfonylamino groups at a pH-valueof between about 8.5 and 10 with dialkyl sulfate. If desired,monoazo-dyestuffs containing N-alkyl-ethionylamino orN-alkyl-fl-c'hloro-ethanesulfonylamino groups prepared according to theprocess of the present invention may also be transformed into theproducts of the present process containing N-alkyl-vinylsulfonylaminogroups of a subsequent treatment with an acid-binding agent.

The monoazo-dyestuifs obtainable by the process of the present inventionare suitable for dyeing and printing natural or regenerated proteinfibers, such as wool and silk, furthermore, polyamide and polyurethanefibers, and especially native and regenerated cellulose material, suchas cotton, linen, staple fiber or artificial silk. The dyeing andprinting of cellulose fibers is carried out advantageously by treatingthe material with an aqueous solution of the dyestuff at normal orelevated temperature in the presence of an acid-binding agent or byprinting with a printing paste in the presence of an acid-binding agentand by subsequently heating and steaming the material.

The monoazo-dyestutfs obtainable by the process of the presentinvention, in practice, possess advantages over the dyestuffs used asstarting material. When dyeing cotton according to the direct dyeingmethod or the socalled padbatch method or when printing cotton, betterresults, especially a higher proportion of dyestuif fixed on the fibrousmaterial, are obtained, comparing the dyestuffs used as startingmaterial with the products obtained in the process of the presentinvention. As a rule, the dyestuffs yield pure dyeings and printsdistinguished by good fastness properties, more particularly, by a goodto very good fastness to light and a very good fastness to wetprocessing.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts and percentages being byweight unless otherwise stated and the relationship of parts by weightto parts by volume being the same as that of the kilogram to the liter.

Example 1 10 parts of the monoazo-dyestuif, obtainable by diazotizing3-amino-1-N-ethionylaminobenzene and coupling the diazo compoundobtained with l-hydroxynaphthalene- -sulfonic acid are dissolved in theform of the potassium salt in 170 parts by volume of water. 30 parts byvolume of dimethyl sulfate and dilute sodium hydroxide solution ordilute potassium hydroxide solution are slowly introduced at 45 C. to 50C. into the vigorously stirred dyestuff solution. The speed with whichthe mixture is introduced is adjusted so as to maintain a pH- value ofbetween 7.2 and 7.5. The mixture is after-stirred for 3 hours at 45 C.to 50 C., and, subsequently, potassium chloride is added. The productprecipitated is separated by filtration at 20 C., washed with potassiumchloride solution and dried in vacuo at 50 C. There is obtained a redpowder which dissolves easily in water to give a red solution.

4 parts of the dyestuff obtained are mixed with 5 parts of urea, themixture is dissolved in 41 parts of water and introduced in 50 parts ofa sodium-alginate-thickening of 4% strength, while stirring. 3 parts ofsodium bicarbonate are then added, and a cotton fabric is printed withthe paste obtained. The fabric is dried and steamed for 5 minutes at C.to 102 C. The material is then rinsed, soaped at boiling temperature,rinsed again and dried. There is obtained an intense red printpossessing a good fastness to boiling.

When using instead of 4 parts of the methylated dyestuff the samequantity of the dyestutf used as starting material, there is obtained adull print of merely very low intensity.

Example 2 31 parts of the dyestuff obtained by coupling diazotized4-amino-1-N-ethionylaminobenzene withl-hydroxynaphthalene-3,6-disulfonic acid are disolved at 40 C. in 250parts by volume of water. For methylating, 50 parts by volume ofdimethyl sulfate and saturated potassium bicarbonate and sodiumcarbonate solution are introduced simultaneously at said temperaturewithin 1 hour, while vigorously stirring, so as to maintain a pH-valueof between 7.0 and 7.4. The mixture is after-stirred for 2 hours at 40C. The methylation is complete when a drop test on filter paper with 2N-soda solution does not show any change of color to violet. The productis salted out at 5 C. with potassium chloride, separated by filtrationand dried in vacuo at 60 C. The dyestuff containing in the dyestuffmolecule an N-methyl-Nethionylarnino group, is obtained in the form of ared brown powder which dissolves easily in water to give a red solution.According to the printing directions for cotton given in Example 1, theproductcontrary to the dyestuif used as starting material--yields anintimate clear scarlet print, the color of which does not change toviolet when dropping dilute soda solution on it.

Example 3 10 parts of the dyestuff prepared by coupling diazotized4-amino-1-N vinylsulfonylaminobenzene with 7-acetylamino-1-hy-droxynaphthalene-3-sulfonic acid are dissolved in thehot in parts by volume of Water. Diethyl sulfate and sodium hydroxidesolution of 20% strength are added slowly at a temperature of between 60and 70 C. and a pH value of between 7.5 and 8, while vigorouslystirring, until the dyestuff used as starting material is completelyethylated. When the reaction is complete, the mixture is cooled down to10 C., and potassium chloride is added. The dyestuff precipitated isisolated by filtration, washed with potassium chloride solution anddried in vacuo. When applying the so-called pad-batchsteaming process,in which sodium carbonate is used as acid-binding agent, and thematerial is steamed for 5 minutes at 100 C. to C., the dyestuif obtainedyields an intense scarlet dyeing possessing a very good fastness towashing.

Example 4 15 parts of the dyestuff used as starting material in Example2 are dissolved at 90 C. in parts by volume of water. 30 parts by volumeof benzyl chloride and 2 N-sodium hydroxide solution are introducedlWlUhiIl 1 hour at a temperature of between 90 C. and 95 C. and apI-Iwalue of 8, while vigorously stirring. The mixture is after-stirredfor 2 hours at the same temperature and at the same pH-value. When thereaction is complete, the mixture is distilled with steam andsubsequently cooled down to room temperature. The benzylated product issalted out with potassium chloride, separated by filtration and dried at60 C. The dyestutf possesses properties similar to those of the dyestuffdescribed in Example 2.

Example 5 15 parts of the dyestuff obtained by diazotizing 4-amino-1-N-ethionylaminobenzene and coupling 8-acetylamino-1-hydroxynap-hthalene-3,6-disulfonic acid are dissolved at 40 C. in 150parts by volume of water. At this temperature, 30 parts by volume ofdimethyl sulfate and 2 N- potassiurn bicarbonate solution are introducedwithin 1 I ll.

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18 3. The process as claimed in claim 1, wherein sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate, sodiumhydrogen carbonate and potassium hydrogen carbonate is used as anacid-binding agent.

References Cited UNITED STATES PATENTS 2,349,749 5/1944 Paul 260556 X3,124,610 3/1964 Larsen 260556 X 3,133,086 5/1964 Bossard et al 260556 X3,234,257 2/1966 Kiihne 260205 X CHARLES B. PARKER; Primary Examiner. D.M. PAPUGA, Assistant Examiner.

US. Cl. X.R.

